agus hadiyarto

Pokok Bahasan
1.
2.
3.
4.
5.

Definisi
Proses Produksi dan Minimisasi Limbah
Evaluasi Kinerja Lingkungan Proses produksi
Bahaya dan Resiko dan Penanganan Bahan Kimia
Unit Operasi pada Pengendalian Pencemaran

Buku Acuan
1. Allen, D.T, Shonnard D.R, 2002, Green
Engineering, Prentice Hall PTR, Upper Saddle
River.
2. Bishop P.L., 2000, Pollution Prevention
Fundamentals and Practice, McGraw-Hill
International Editions, Boston
3. Clark J, Macquarrie D (ed), 2002, Handbook of
Green Chemistry & Technology, Blackwell
Publishing,London
4. Tavlarides LL , 1985, Process Modifications for
Industrial Pollution Source Reduction, Lewis
Publishers., Inc., Michigan

Definisi TEKNOLOGI BERSIH

Semua jenis upaya menghasilkan produk,
melakukan proses dan service yang dapat
mengurangi penggunaan sumberdaya alam
dan atau mengurangi terbentuknya limbah
maupun terjadinya pencemaran lingkungan

TIPE PROSES PRODUKSI

Bahan
baku
Energi

Produk

Proces
s
Limbah ke
lingkunga
n

Praktek Industri Masa Lampau

Produk

Bahan baku

Process
Energi

Residual

3R

Waste

Resikel
Produk
samping

Praktek Industri Masa Kini

Treatment

Sisa Limbah
ke
lingkungan

Bahan
baku
Energi

Produk

Process

Residual

Residuals

3R

Reprocess

Process

Resikel
Produk
samping
Resikel

Praktek Industri Yang Ideal

3R

Input

Proses

Output
Produk Akhir
yang
diinginkan

Bahan Mentah
Energi

Timbulan KBP

Air

Biaya Input KBP

Biaya untuk
Proses KBP

Pe
mb
ua
KB nga
n
P

Biaya
Pembuangan
KBP

Non-product
output (KBP)

10-30%
dari total
biaya Produksi

Total Biaya
KBP

KBP
KBP==Semua
Semuabahan
bahan/materi,
/materi,energi
energidan
danair
airyang
yangdigunakan
digunakandalam
dalamproses
prosesproduksi
produksitetapi
tetapi
tidak
tidakmasuk
masuk sebagai
sebagaibagian
bagian dari
dariproduk
produkakhir.
akhir.
Sumber : KLH-

Tugas kelompok (max 2

orang)
Identifikasi NPO di pabrik
kimia (input, proses, output)

Waste Minimisation = Pollution

Prevention

11/30/15

Source Reduction -1R

Recycle, Reuse, Recovery - 3R

Waste Treatment

Secure Dispose

10

Source Reduction
1.

Product Change
Design for less environmental impact
Increase product life

2.

Process Changes
Input Material Changes
Technology Changes
Improved Operating Practices

11

Process Changes
2.1. Input Material Changes
Material Purification
Substitution of less toxic materials
2.2. Technology Changes
Lay Out Changes
Increase Automation
Improved Operating Conditions
Improved Equipment
New Technology
12

Process Changes
2.3. Improved Operating Practices

Operating and Maintenance Procedure

Management Practices

Stream Segregation

Material Handling Improvements

Production Scheduling

Inventory Control

Training

Waste Segregation

13

Recycle Reuse - Recovery

In process recycle unreacted feed is
separated and recycled back to the reactor
On site recycle waste from the reactor is
converted to a commercial product by a second
reactor within the facility
Off site recycle - waste from the reactor is
separated and then transferred off-site where it is
converted to a commercial product within another
facility

Waste definition
as a non product left over at the end of a
process or action (generic)
industrial waste :
as materials coming from a manufacturing
process that are not directly used within
the corporation and that are marked for
disposal or release to the environment
(Graedel and Allenby, 1995)
is a resource out of place (Bishop, PL, 2000)
11/30/15

15

Wastewater Treatment
1. Physical; Chemical; Biochemical/Bioremediation ; Phytoremediation;
2. Combination (P-C-Bc-PyR), Ion Exchange, Plasma

1. Absorption; Adsorption; Combustion; Condensation; BioFiltration

2. Wet Scrubber, Filter Chamber, ESP

1. Landfiil, Composting, Sanitary control landfil, Pyrolisis, Gasification

16

Waste treatment (liquid, solid,

gas/particulate)
Liquid : (1) Fisis (segregasi, sedimentasi , screening,mikro
filtrasi, nano filtrasi,) ; (2) Kimia (koagulasi,oksidasi,
insinerasi, gasifikasi, pirolisis) ; Fotokimia (plasma); (3)
Biokimia/Bioremediasi (aerob, anaerobic) (4)
Fitoremediasi; (5) Kombinasi (F-K-B-FR)
Solid : (1) Komposting, (2) Controll Sanitary Landfill, (3)
Pirolisis, (4) Gasifikasi (5) Incineration, (6) Solidifikasi
Gas/Vapor : (1) Absorpsi; (2) Adsorpsi; (3) Kombusi; (4)
Kondensasi; (5) BioFiltrasi;
Particulate : (1) ESP; (2) Filter chamber (3) Cyclone
Separator
17

Secure Disposal
1. Enkapsulasi
2. Injeksi ke dalam sumur tidak
produktif
3. Pembuangan ke lapisan
hipolimnion

18

Evaluating Environmental
Performance During Process
Synthesis

1. Economic Criteria
Two alternative processes for the manufacture of methyl
methacrylate.
1.Can be manufactured through an acetone-cyanohydrin
pathway.
(CH3)2C=O + HCN HO-C(CH3)2-CN
Aceton + Hydrogen Cyanide Acetone Cyanohydrin
HO-C(CH3)2-CN + H2SO4 CH3-(C=CH2)-(C=O)NH2(H2SO4)
acetone cyanohydrin methacrylamide sulfate

The methacrylamide sulfate is then cracked, forming

methacrylic acid and methyl-methacrylate
CH3-(C=CH2)-(C=O)-NH2(H2SO4) + CH3OH CH3-(C=CH2)(C=O)-OH CH3-(C=CH2)-(C=O)-O-CH3
2. Alternatively, methyl methacrylate can be manufactured
with
isobutylene and oxygen as raw materials
CH3-(C=CH2)-CH3 + O2 CH3-(C=CH2)-(C=O)H + H2O
isobutylene + oxygen methacrolein

CH3-(C=CH2)-CH3 + O2 CH3-(C=CH2)-(C=O)H + H2O

isobutylene

+ oxygen methacrolein

CH3-(C=CH2)-(C=O)H + 2O2 CH3-(C=CH2)-(C=O)-OH

methacrolein

+ oxygen methacrylic acid

CH3-(C=CH2)-(C=O)-OH + CH3OH CH3-(C=CH2)-(C=O)-OCH3 +

H2 O
methacrylic acid + methanol (in sulfuric acid)
methylmethacrylate

Stoichiometric and Cost Data for Two Methyl

Methacrylate Synthesis Routes
Compound

Pounds produced or pounds of

raw material required per pound
of methyl methacrylate

Cost ($)
per
pound

Acetone-cyanohydrin
route
Acetone

- 0.68

0.43

Hydrogen Cyanide

- 0.32

0.67

Methanol

- 0.37

0.064

Sulfuric Acid

- 1.63

0.04

1.00

0.78

Isobutylene

- 1.12

0.31

Methanol

- 0.38

0.064

Pentane

- 0.03

0.112

Sulfuric acid

- 0.01

0.04

Methyl Methacrylate
Isobutylene route

The raw material costs per pound of methyl

methacrylate are :

(0.68x$0.43)+(0.32x$0.67)+(0.37x$0.064)+(1.63x$0.04) =
$0.60 per pound of methyl methacrylate

For isobutylene route, a similar calculation leads to a cost of

$0.37 per pound of methyl methacrylate

It is clear that the isobutylene route has lower raw material

costs than the acetone-cyanohydrin route, and is probably
economically preferable.

2. Environmental Criteria
One set of environmental criteria that can be
rapidly estimated, even at the input-output level
of design, are the persistence,
bioaccumulation, and toxicities of the input
and output materials.
Persistence and bioaccumulation for each of the
compounds listed in below table.
In this case, all of the compounds would have
persistence ratings of 1 and bioaccumulation
ratings of 1

Bioaccumulation and Persistence Data for Two

Synthesis Routes
Aquatic half
life
(biodegradatio
n index)

Bioaccumulatio
n
(bioconcentrati
on factor)

52 days

weeks

3.2

1 year

weeks

3.2

17 days

days-weeks

3.2

7 hours

weeks

2.3

2.5 hours

weeks

12.6

Methanol

17 days

days-weeks

3.2

Pentane

2.6 days

days-weeks

81

Compound

Persistence
(atmospheric
half life)

Acetone-cyanohydrin route
Acetone
Hydrogen Cyanide
Methanol
Sulfuric Acid
Methyl Methacrylate
Isobutylene route
Isobutylene

Sulfuric acid
Methyl methacrylate

7 hours

weeks

2.3

Classification Schemes for Persistence

and Bioaccumulation
Persistence
Rapid

> 60% degradation over 1 week

Rating index =
0

Moderate

> 30% degradation over 28 days

Rating index =
1

Slow

< 30% degradation over 28 days

Rating index =
2

Very Slow

< 30% degradation over more than 28

days

Rating index =
3

High Potential

8.0 > Log Kow >4.3

1000

Rating index =
3

Moderate
Potential

4.3 > Log Kow > 3.5

1000>BCF>250

Low Potential

3.5 > Log Kow

BCF

Bioaccumulatio
n
or BCF >
or

Rating index =
2
or 250 >

Rating index =
1

Pollution Prevention in material

selection for unit operations

Example :
Compare the emission of SO2 resulting from the combustion of three fuel types that will satisfy an
energy demand of 106 BTU. The fuel types are No.6 fuel oil (FO), No.2 fuel oil and natural gas. The
elemental composition by weight for each fuel are listed below along with the density and lower
heating value.
No.6 FO

No.2 FO

Natural gas

Density, lb/ft3

61.23

53.66

0.0485

Lower Heating Value, BTU/gal

148,000

130,000

1060 BTU/cuft

Carbon, wt%

87.27

87.30

74.8

Hydrogen, wt%

10.49

12.60

25.23

Sulfur, wt%

0.84

0.22

Oxygen, wt%

0.64

0.04

0.0073

Nitrogen, wt%

0.28

0.006

Ash, wt%

0.04

<0.01

Solution
The volume of No.6 FO needed is (106 BTU/148,000 BTU/gal) = 6.76 gal
The mass of No.6 FO needed is (6.76 gal)(1 cuft/7.48 gal)(61.23 lb/cuft) = 55.18 lb
The mass of SO2 generated is (55.31 lb)(0.0084 lbS/lb)(64.06 lbSO 2/32.06 lbS)=0.928 lb SO2

Hazard assessment of chemical carcinogenic

(US EPA)
Gro
up
A

Carcinogenic to humans (there are currently only about 20 of these

chemicals

B1

Probably carcinogenic to humans based on limited human evidence

of carcinogenicity

B2

Probably carcinogenic to humans based on sufficient animal

evidence, but in adequate human evidence

Possibly carcinogenic to humans

Not classifiable for human carcinogenicity

E
Evidence of noncarcinogenicity for humans
Occupational Safety and Health Administration (OSHA) have thirteen chemical
subtances, by name and CAS number as human carcinogenic.
American Conference of Govermental Industrial hygienists (ACGIH) non
govermental organization, also classify chemicals according to the evaluated
risk for human carcinogenicity

Thirteen OSHA Regulated carcinogens (29CFR

1910.1003)
CAS
Number

Chemical Name

Pervious Use

53-96-3

2-acetylaminofluorene

Hazardous air pollutant-no use

92-67-1

4-aminodiphenyl

Antifungal agent

92-87-5

Benzidine

Manufacture of azo dyes

542-88-1

Bis-chloromethyl ether

Manufacturing ion exchange resins

91-94-1

3,3-dichlorobenzidine

Manufacture of azo dyes, yellow

pigments

60-11-7

4-dimethylaminoazobenzene

Ph indicator

151-56-4

Ethyleneimine

Treatment (etherification) of cotton

107-30-2

Methyl chloromethyl ether

Manufacturing ion exchange resins

134-32-7

Alpha-naphthylamine

Manufacturing dyes

91-59-8

Beta- naphthylamine

Manufacturing dyes

92-93-3

4-nitrobiphenyl

Manufacturing p-biphenylamine

62-75-9

N-nitrosodimethylamine

Antioxidant in lubricants,polymer
softener

57-57-8

Beta-propiolactone

disinfectant

Octanol-water Partition Coefficient, Kow

Specialized parameters used in environmental fate

The octanol water partition coefficient is used to characterize the
partitioning of a molecule tween largely aqueous phases, such as
rivers and lakes, and largely hydrophobic phase, such as the
organic fraction of sediments suspended in water bodies.

Log Kow = 0,229 + ni.fi + ni.ci

ni = is the number of groups of type in the molecule

fi = is the contribution of each group to the partition coefficient
nj = is the number of groups of type j in the molecules
ci = is the correction factor for each group

TLVs, PELs, RELs

Is one type of airborne concentration limit for individual
exposures in the workplace environment. The concentration is
set at a level for which no adverse effect would be expected
over a workers life time
TLVs (Threshold Limit Values)
The TLVs will be time-weighted averages for an 8-hour workday and a 40-hour workweek.
TLVs are established NGO (the American Conference of Governmental Industrial
Hygienists (ACGIH).

PELs (Permissible Exposure Limits)

The United States Occupational Safety and Health (OSHA) has the legal authority to place
limits on exposures to chemicals in the workplace.

RELs (Recomended Exposure Limits)

The National Institute for Occupational safety and Health (NIOSH), under the Centers for
Disease Control and Prevention (CDC) publishes RELs based on toxicity research.
TLVs, PELs, RELs, value are generally quite similar, but some of the difference are worthy
of comment. TLV value represent a scientific and professional assessment of hazard,
while PEL value have legal implication in defining workplace condition. Because of
these legal implication , PELs are directly influenced by political, economic and
feasibility issues.

Three types of TLVs for chemical substances

Threshold limit value - Time weighted average
(TLV-TWA): average exposure on the basis of a
8h/day, 40h/week work schedule
Threshold limit value - Short-term exposure limit
(TLV-STEL): spot exposure for a duration of 15
minutes, that cannot be repeated more than 4
times per day
Threshold limit value - Ceiling limit (TLV-C):
absolute exposure limit that should not be
exceeded at any time

There are TLVs for physical agents as well

as chemical substances. TLVs for physical
agents include those for noise exposure,
vibration, ionizing and
non-ionizing radiation exposure and heat
and cold stress.

TLVs
Response

LD50
ED
TWA

Threshold

Safety 5120

Dose

Industrial Hygiene

OSHA (PELs) ACGIH

(TLVs)
Chemical
PEL
TLV (2007)
Acetylaldehyde
200 ppm
25 ppm
Acetic Acid 10 ppm
10 ppm
Acetone
1000 ppm
500
Itsppm
units are in parts per million (ppm) for gases and in milligrams per
cubic meter (mg/m) for particulates such as dust, smoke and mist

Safety 5120

Industrial Hygiene

NIOSH (RELs)-ACGIH
(TLVs)
Chemical
RELs
TLVs (2007)
Acetylaldehyde
18 ppm
25
ppm
Acetic Acid
10 ppm
10 ppm
Acetone
250 ppm
500 ppm

Safety 5120

Industrial Hygiene

German MAKs
In the work-place environment MAK
values (maximum allowable workplace
concentrations) haven been fixed as
time-integrated averages relatively early
in order to avoid adverse health effects to
workers exposed to air pollution during
their working shift.

Safety 5120

Industrial Hygiene

GERMAN MAKs
Acetaldehyde

: 5 mg/m3

Acetanilide

: 6 mg/m3

Acetic acid

: 15mg.m3

Acetic anhydride

: 10mg/m3

Acetone

: 200 mg/m3

The basic formula for converting between ppm and mg/m for
gases is ppm = (mg/m3) x 24.45 / molecular weight

Safety 5120

Industrial Hygiene

TLV - STELS
Short Term Exposure Limits
15 minutes
Never exceeded at any time
STEL Is the level one can be exposed
to without irritation, chronic effects or
dose related toxic effects

Safety 5120

Industrial Hygiene

Similar concepts

The TLV is equivalent in spirit, although the materials covered, values

recommended, and definitions used can differ, to the following concepts.
WEEL (Workplace environmental exposure level) created by a committee of
the American Industrial Hygiene Association AIHA
Similar concepts used in other countries include:
Australia

France

VME (Valeur Moyenne d'Exposition )

VLE (Valeur Limite d'Exposition )

Germany

OES Occupational exposure standard [1]

AGW (Arbeitsplatzgrenzwert trans. Workplace Limit Value)

MAK (Maximale Arbeitsplatz-Konzentration trans. Maximum Workplace
Concentration)

Similar concepts

Malaysia

Netherlands

NDN (Najwysze Dopuszczalne Natenie)

Russia

WES (Workplace Exposure Standards)

Poland

MAC (Maximaal Aanvaarde Concentratie trans. Maximum Accepted

Concentration)

New Zealand

PEL (Permissible exposure limit)

( )

IDLH (Immediately Dangerous to Life or

Health)
Defined by the US
National Institute for Occupational Safety and Health (NIOSH)
as exposure to airborne contaminants that is "likely to cause
death or immediate or delayed permanent adverse health
effects or prevent escape from such an environment."
Examples include smoke or other poisonous gases at
sufficiently high concentrations.
The OSHA regulation (1910.134(b)) defines the term as "an
atmosphere that poses an immediate threat to life, would
cause irreversible adverse health effects, or would impair an
individual's ability to escape from a dangerous atmosphere." [1]
IDLH values are often used to guide the selection of breathing
apparatus that are made available to workers or firefighters in
specific situations.

Substance
Acetaldehyde
Acetic acid(Vinegar)
Acetone
Acrolein (used in chemical weapons)

IDLH
2000 ppm
50 ppm
2500 ppm
2 ppm

Ammonia
Arsine
Benzene

300 ppm
3 ppm
500 ppm

Benzyl chloride (used in chemical

weapons)

10 ppm

Substance
Bromine
Carbon dioxide
Carbon monoxide
Carbon tetrachloride (Halon/Freon)
Chlorine (used in chemical weapons)
Chlorine dioxide
Chlorine trifluoride
Chloroform
Chloropicrin (used in chemical
weapons)
Diazomethane
Diborane
Dimethyl sulfate (used in chemical
weapons)
Disulfur decafluoride (about 4 times as
poisonous as phosgene)
Ethanol (alcohol found in alcoholic
beverages)

IDLH
3 ppm
40000 ppm (4% in a volume of air)
1200 ppm
200 ppm
10 ppm
5 ppm
20 ppm
500 ppm
2 ppm
2 ppm
15 ppm
7 ppm
1 ppm
3300 ppm

Substance
Fluorine
Formaldehyde
Hydrogen cyanide
Hydrogen selenide
Hydrogen Sulfide
Iodine
Isopropyl alcohol
Methyl alcohol
Methyl isocyanate
Nickel carbonyl
Nickel tetracarbonyl
Nitric acid
Nitric oxide
Nitrogen dioxide
Octane
Ozone
Pentaborane
Phenol

IDLH
25 ppm
20 ppm
50 ppm
1 ppm
100 ppm
2 ppm
2000 ppm
6000 ppm
3 ppm
2 ppm
30 ppm
25 ppm
100 ppm
20 ppm
1000 ppm
5 ppm
1 ppm
250 ppm

Substance
Phosgene (used in chemical
weapons)
Phosphine
Propane
Selenium hexafluoride
Soman or Cyclosarin[4]
Stibine
Styrene
Sulfur dioxide
Sulfur mustard[3]
Tabun or Sarin[4]
Tellurium hexafluoride
Tetramethylsuccinonitrile
Tetranitromethane
Toluene
Toluene diisocyanate
Trifluorobromomethane
Turpentine
VX[4]

IDLH
2 ppm
50 ppm
2100 ppm
2 ppm
0.05 ppm
5 ppm
700 ppm
100 ppm
0.7 ppm
0.1 ppm
1 ppm
5 ppm
4 ppm
500 ppm
2.5 ppm
40000 ppm
800 ppm
0.003 ppm